U.S. patent number 4,889,664 [Application Number 07/276,007] was granted by the patent office on 1989-12-26 for method of forming shaped hydrogel articles including contact lenses.
This patent grant is currently assigned to Vistakon, Inc.. Invention is credited to John C. Heaton, Ture Kindt-Larsen, Edmund C. Rastrelli.
United States Patent |
4,889,664 |
Kindt-Larsen , et
al. |
December 26, 1989 |
Method of forming shaped hydrogel articles including contact
lenses
Abstract
Shaped hydrogel articles such as soft contact lenses are
prepared by (1) molding or casting a polymerization mixture
comprising: (a) a monomer mixture comprising a major proportion of
a hydrophilic (meth)acrylate ester such as 2-hydroxyethyl
methacrylate, and a cross-linking monomer; and (b) a
water-displaceable diluent, wherein said diluent has a viscosity of
at least 100 MPa Sec at 30.degree. C., and wherein said diluent
consists essentially of a boric acid ester of certain dihydric
alcohols, said dihydric alcohols having Hansen polar
(.delta..sub.p) and Hansen hydrogen bonding (.delta..sub.h)
cohesion parameters falling within the area of a circle defined as
having a center at .delta..sub.h =20.5, .delta..sub.p =13, and a
radius of 8.5, to produce a shaped gel of a coploymer of said
monomers and said diluent, and (2) thereafter replacing said
diluent with water.
Inventors: |
Kindt-Larsen; Ture (Vedbaek,
DK), Heaton; John C. (Jacksonville, FL),
Rastrelli; Edmund C. (Jacksonville, FL) |
Assignee: |
Vistakon, Inc. (Jacksonville,
FL)
|
Family
ID: |
23054749 |
Appl.
No.: |
07/276,007 |
Filed: |
November 25, 1988 |
Current U.S.
Class: |
264/2.6; 264/41;
264/233; 264/344; 523/106; 523/108; 524/548; 524/558; 524/701;
524/809; 524/850; 524/853 |
Current CPC
Class: |
B29D
11/00038 (20130101); G02B 1/043 (20130101); B29K
2033/08 (20130101); B29K 2105/0002 (20130101); B29K
2033/12 (20130101); B29K 2707/02 (20130101); B29K
2995/0092 (20130101) |
Current International
Class: |
B29D
11/00 (20060101); G02B 1/04 (20060101); B29D
011/00 () |
Field of
Search: |
;264/2.6,41,233,344
;523/106,108 ;524/548,558,701,809,850,853 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lowe; James
Attorney, Agent or Firm: Metz; Charles J.
Claims
What is claimed is:
1. Process for producing shaped hydrogel articles which comprises
the steps of:
(1) molding or casting a polymerization mixture comprising:
(a) a monomer mixture comprising a major proportion of a
hydrophilic (meth)acrYlate ester monomer and a cross-linking
monomer; and
(b) a water-displaceable diluent, wherein said diluent has a
viscosity of at least 100 MPa Sec at 30.degree. C., and wherein
said diluent consists essentially of a boric acid ester of certain
dihydric alcohols, said dihydric alcohols having Hansen polar
(.delta..sub.p) and Hansen hydrogen bonding (.delta..sub.h)
cohesion parameters falling within the area of a circle defined as
having a center at .delta..sub.h =20.5, .delta..sub.p =13, and a
radius of 8.5, to produce a shaped gel of a copolymer of said
monomers and said diluent, and
(2) thereafter replacing said diluent with water.
2. The process of claim 1 wherein the said hydrophilic monomer is a
hydroxyalkyl (meth)acrylate.
3. The process of claim 2 wherein the hydroxyalkyl (meth)acrylate
is 2-hydroxyethyl methacrylate.
4. The process of claim 1 wherein said diluent has a viscosity of
at least 500 MPa Sec at 30.degree. C.
5. The process of claim 1 wherein said dihydric alcohol is selected
from the group consisting of ethylene glycol, 1,2-propanediol,
1,4-butanediol, 1,6-hexanediol, 2,5-hexanediol, 1,8-octanediol,
diethylene glycol, triethylene glycol, tetraethylene glycol,
polyethylene glycol having a molecular weight of up to about 2000,
dipropylene glycol, and tripropylene glycol.
6. The process of claim 4 wherein said dihydric alcohol is selected
from the group consisting of 1,4-butanediol, 1,6-hexanediol,
2,5-hexanediol, diethylene glycol, triethylene glycol,
tetraethylene glycol, polyethylene glycol having a molecular weight
of up to about 1000, dipropylene glycol, and tripropylene
glycol.
7. The process of claim 1 wherein said dihydric alcohol is
1,4-butanediol.
8. The process of claim 1 wherein said dihydric alcohol is
diethylene glycol.
9. The process of claim 1 wherein the monomer mixture contains
methacrylic acid.
10. The process of claim 1 wherein the shaped hydrogel article is a
contact lens.
11. The process for producing contact lenses which comprises the
steps of:
(1) molding or casting a polymerization mixture comprising:
(a) a monomer mixture comprising a major proportion of a
hydrophilic (meth)acrylate ester, a cross-linking monomer, and a
hydrophobic monomer; and
(b) a water-displaceable diluent, wherein said diluent has a
viscosity of at least 100 MPa Sec at 30.degree. C., and wherein
said diluent consists essentially of a boric acid ester of certain
dihydric alcohols, said dihydric alcohols having Hansen polar
(.delta..sub.p) and Hansen hydrogen bonding (.delta..sub.h)
cohesion parameters falling within the area of a circle defined as
having a center at .delta..sub.h =20.5, .delta..sub.p =13, and a
radius of 8.5, to produce a shaped gel of a copolymer of said
monomers and said diluent, and
(2) thereafter replacing said diluent with water.
12. The process of claim 11 wherein the said hydrophilic monomer is
a hydroxyalkyl (meth)acrylate.
13. The process of claim 12 wherein the hydroxyalkyl (meth)acrylate
is 2-hydroxyethyl methacrylate.
14. The process of claim 11 wherein said diluent has a viscosity of
at least 500 MPa Sec at 30.degree. C.
15. The process of claim 11 wherein said dihydric alcohol is
selected from the group consisting of ethylene glycol,
1,2-propanediol, 1,4butanediol, 1,6-hexanediol, 2,5-hexanediol,
1,8-octanediol, diethylene glycol, triethylene glycol,
tetraethylene glycol, polyethylene glycol having a molecular weight
of up to about 2000, dipropylene glycol, and tripropylene
glycol.
16. The process of claim 14 wherein said dihydric alcohol is
selected from the group consisting of 1,4-butanediol,
1,6-hexanediol, 2,5-hexanediol, diethylene glycol, triethylene
glycol, tetraethylene glycol, polyethylene glycol having a
molecular weight of up to about 1000, dipropylene glycol, and
tripropylene glycol.
17. The process of claim 11 wherein said dihydric alcohol is
1,4-butanediol.
18. The process of claim 11 wherein said dihydric alcohol is
diethylene glycol.
19. The process of claim 11 wherein the monomer mixture contains
methacrylic acid.
20. The process of claim 11 wherein the hydrophobic monomer is a
benzotriazole ester.
21. The process of claim 20 wherein the benzotriazole ester is
2-(2'-hydroxy-5'-methacryloxypropyl-3'-tert-butylphenyl)-5-chloro-2H-benzo
triazole.
Description
The invention relates to the production of shaped hydrogel articles
including soft contact lenses, and more particularly to a method
for the direct molding of such articles using certain boric acid
esters as water-displaceable diluents.
BACKGROUND OF THE INVENTION
Until recently, soft contact lenses of the hydrogel type have been
manufactured either by lathe cutting or spin casting. In the lathe
cutting method, a lens blank or button of a substantially anhydrous
hydrophilic polymer (xerogel) is mechanically cut and polished to a
lens shape on a fine lathe, and thereafter is contacted with water
or saline to hydrate the polymer and form the desired hydrogel
lens. The mechanical steps utilized in the lathe cutting operation
are similar to those used in the manufacture of hard contact
lenses, except that allowance must be made for swelling of the lens
during hydration of the polymer.
In the spin casting method, a small quantity of hydrophilic monomer
mixture is placed in a concave, optically polished mold, and the
mold is rotated while the monomers are polymerized to form a
xerogel lens. The two optical surfaces of the lens are formed
simultaneously during polymerization, the outer surface being
formed by the concave mold surface and the inner surface being
shaped by the joint actions of centrifugal force generated by the
rotating mold and surface tension of the polymerization mixture.
The lens produced thereby is contacted with water or saline to
hydrate the polymer and form a hydrogel lens as in the case of the
lathe cut lens.
More recently, an improved process for producing hydrogel contact
lenses has been developed, which method is not only more economical
than either the lathe cut method or the spin casting method, but it
has the advantage of enabling a more precise control over the final
shape of the hydrated lens. This new method comprises the direct
molding of a monomer mixture wherein said mixture is dissolved in a
non-aqueous, water-displaceable solvent, the mixture is placed in a
mold having the shape of the final desired hydrogel (i.e.,
water-swollen) lens, and the monomer/solvent mixture is subjected
to conditions whereby the monomer(s) polymerize, to thereby produce
a polymer/solvent mixture in the shape of the final desired
hydrogel lens. (The polymerization must be carried out in a
non-aqueous medium because water inhibits the polymerization
reaction ) After the polymerization is complete, the solvent is
displaced with water to produce a hydrated lens whose final size
and shape are quite similar to the size and shape of the original
molded polymer/solvent article. Such direct molding of hydrogel
contact lenses is disclosed in Larsen, U.S. Pat. No. 4,495,313 and
in Larsen et al., U.S. Pat. No. 4,680,336.
In the Larsen patent, the water-displaceable diluents used are
boric acid esters of polyhydric alcohols wherein the polyhydric
alcohols have three or more hydroxyl groups. Alternatively, the
polyhydric alcohols used may be a mixture of a polyhydric alcohol
having three or more hydroxyl groups and a dihydric alcohol. See,
for instance, the disclosure at Col. 3, lines 60 et seq. and Col.
4, lines 18-22.
The clear teaching of the Larsen patent is that the polyhydric
alcohol used to prepare the borate esters for use in the direct
molding process of hydrogel contact lenses must have three or more
hydroxyl groups. While it is disclosed that dihydric alcohols can
be used in admixture with tri- and higher polyols, the tri- and
higher polyols are essential components.
This invention is based on the discovery that esters of boric acid
and certain dihydric alcohols (as more fully defined below) can be
used as water-displaceable diluents in a direct molding process for
making shaped hydrogel articles such as soft contact lenses from
polymer mixtures containing as the principal monomer one or more
hydrophilic (meth)acrylates such as 2-hydroxyethyl methacrylate
("HEMA"). The invention provides processing advantages in the
direct molding process for producing shaped hydrogel articles,
including enhanced demoldability (i.e., the ability to open the
mold after the polymerization with less force), which results in
economic advantages such as a saving of labor costs, and a
significant increase in yield because of a reduced proportion of
surface defects in the molded articles that would cause rejection.
It is believed that the enhanced demoldability and significant
improvement in yield is related to the fact that the boric acid
esters of diols that are employed in this invention have a lower
surface tension than the preferred esters of the Larsen patent, No.
4,495,313, which reduces the adhesion of the polymer/solvent
mixture to the mold.
An additional significant advantage that is imparted to the direct
molding process by the water-displaceable esters provided by this
invention is an enhanced ability to employ hydrophobic monomers
(such as UV-absorbing monomers) in the polymerization mixture. When
one tries to include hydrophobic monomers such as UV-absorbing
monomers in a monomer/diluent mixture using as the diluent the
preferred esters of the said Larsen patent, it is found that the
hydrophobic monomers are often not soluble in the mixture.
Increasing medical awareness of the adverse affects of ultraviolet
("UV") radiation on the eyes has led to the introduction of
spectacles, goggles, contact lenses, and intraocular lenses
containing a means to absorb UV radiation. With respect to both
contact lenses and intraocular lenses made from polymers (usually
acrylic polymers), the preferred means for imparting UV absorbing
capability is to make the lens from a copolymer that contains a
copolymerized UV-absorbing monomer. Such monomers are disclosed,
for example, in Beard et al., U.S. Pat. No. 4,528,311 and Dunks et
al., U.S. Pat. No. 4,716,234. It would be desirable to impart
UV-absorbing properties to contact lenses made by the direct
molding process by including UV-absorbing monomers in the
monomer/diluent mixture. This invention makes this desired end
practical.
BRIEF SUMMARY OF THE INVENTION
Shaped hydrogel articles such as soft contact lenses are prepared
by the steps of:
(1) molding or casting a polymerization mixture comprising:
(a) a monomer mixture comprising a major proportion of one or more
hydrophilic (meth)acrylate monomers such as 2-hydroxyethyl
methacrylate, and one or more cross-linking monomers; and
(b) a water-displaceable diluent, wherein said diluent has a
viscosity of at least 100 MPa Sec at 30.degree. C., and wherein
said diluent consists
essentially of a boric acid ester of certain
dihydric alcohols, said dihydric alcohols having
Hansen polar .delta..sub.p) and Hansen hydrogen bonding
(.delta..sub.h) cohesion parameters falling within the area of a
circle defined as having a center at .delta..sub.h =20.5,
.delta..sub.p =13, and a radius of 8.5, to produce a shaped gel of
a copolymer of said monomers and said diluent, and
(2) thereafter replacing said diluent with water.
In an important aspect of the invention, soft contact lenses are
prepared by the steps of:
(1) molding or casting a polymerization mixture comprising:
(a) a monomer mixture comprising a major proportion of a
hydrophilic (meth)acrylate monomer such as 2-hydroxyethyl
methacrylate, one or more cross-linking monomers, and a hydrophobic
monomer such as a UV-absorbing monomer; and
(b) a water-displaceable diluent, wherein said diluent has a
viscosity of at least 100 MPa Sec at 30.degree. C., and wherein
said diluent consists essentially of a boric acid ester of certain
dihydric alcohols, said dihydric alcohols having Hansen polar
.delta..sub.p) and Hansen hydrogen bonding (.delta..sub.h) cohesion
parameters falling within the area of a circle defined as having a
center at .delta..sub.h =20.5, .delta..sub.p =13, and a radius of
8.5, to produce a shaped gel of a copolymer of said monomers and
said diluent, and
(2) thereafter replacing said diluent with water.
THE PRIOR ART
The Larsen patent (No. 4,495,313) cited above is the most relevant
prior art known to Applicants.
The Larsen et al. patent, No. 4,680,336, discloses the use in a
direct molding process for making hydrogel articles of certain
diluents that are selected on the basis of their viscosity and
their Hansen polar and hydrogen bonding cohesion parameters.
Other U.S. patents relating to the direct molding of hydrogel
articles such as soft contact lenses include Larsen, U.S. Pat. Nos.
4,565,348 and 4,640,489, Ohkada et al., 4,347,198, Shepard,
4,208,364, and Wichterle et al., Re. 27,401 (3,220,960).
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a plot of the Hansen cohesion parameters, .delta..sub.h
and .delta..sub.p, for several dihydric alcohols;
FIG. 2 is a calibration graph used in the determination of the
Young's modulus of soft contact lenses; and
FIG. 3 is a side view, partially schematic, of the test fixture and
assembly used to determine the force required to open the molds in
which contact lenses comprising polymer/diluent mixtures were
produced.
DETAILED DESCRIPTION OF THE INVENTION
The boric acid esters are esters that are used in the invention as
water-displaceable diluents in the direct molding of hydrogel
articles comprise borate esters of certain dihydric alcohols, said
dihydric alcohols having Hansen polar (.delta..sub.p) and Hansen
hydrogen bonding (.delta..sub.h) cohesion parameters falling within
the area of a circle defined as having a center at .delta..sub.h
=20.5, .delta..sub.p =13, and a radius of 8.5. It is also required
that the ester of boric acid and the dihydroxy compound have a
viscosity of at least 100 MPa Sec at 30.degree. C., and preferably
at least about 500 MPa sec at 30.degree. C.
The boric acid esters are prepared by procedures analogous to those
that are known in the art, as by reacting boric acid with the
dihydric alcohol (for brevity, dihydric alcohols will occasionally
be referred to herein as "diols") and removing the water formed by
the reaction by normal procedures such as by vacuum distillation.
The reaction of boric acid with the dihydric alcohol is carried out
at a temperature and for a period of time sufficient to form the
ester. Typical reaction temperatures are usually found within the
range of from about 50.degree. to about 120.degree. C. At these
temperatures, reaction times of from about two to about twelve
hours are typical. In any event, the reaction is continued until
the water content of the ester is less than about 2%, by weight.
The proportion of boric acid to dihydric alcohol is selected so
that the viscosity of the ester is at least 100 MPa Sec at
30.degree. C. The examples, below, give representative proportions
of boric acid to dihydric alcohol that have been found to give the
desired viscosity in the ester product. In certain cases, it may be
desirable to include a small proportion of a monohydric alcohol in
the esterification reaction mixture to control the molecular weight
of the ester product.
The dihydric alcohols used in preparing the water-displaceable
borate ester diluents used in the invention are those having Hansen
polar (.delta..sub.p) and Hansen hydrogen bonding (.delta..sub.h)
cohesion parameters falling within the area of a circle defined as
having a center at .delta..sub.h =20.5, .delta..sub.p =13, and a
radius of 8.5. The Hansen cohesion parameter .delta. is usually
expressed in terms of three components .delta..sub.h,
.delta..sub.p, .delta..sub.d) where .delta..sub.h is the hydrogen
bonding cohesion parameter, .delta..sub.p is the polar cohesion
parameter, and .delta..sub.d is the dispersion cohesion parameter.
It has been found that for the purposes of this invention the
dispersion cohesion parameters of the dihydric alcohols are
substantially the same (the values that have been determined vary
between about 15.7 and 17.0), and therefore have little effect in
determining the suitability of any particular dihydric alcohol for
use in the invention. The consideration of the Hansen cohesion
parameters for the dihydric alcohol used in making the borate ester
diluent is accordingly reduced to a two-dimensional function on the
basis of polar and hydrogen bonding cohesion parameters.
Hansen cohesion parameters are known in the art. Reference is made
to "CRC Handbook of Solubility Parameters and Other Cohesion
Parameters", by Allan F. M. Barton, CRC Press, Inc., Boca Raton,
Fla. (1983), especially pages 85-87, 141, and 153-164, Hansen, "THE
UNIVERSALITY OF THE SOLUBILITY PARAMETER", I&EC Product
Research and Development, Vol. 8, No. 1, March 1969, pages 2-11,
Wernick, "Stereographic Display of Three-Dimensional Solubility
Parameter Correlations", Ind. Eng. Chem. Prod. Res. Dev., Vol. 23,
No. 2, 1984, pages 240-245, and Kirk-Othmer Encyclopedia of
Chemical Technology, 2nd ed., Suppl. Vol., Interscience, NY 1971,
pages 891 and 892, for illustrative discussions of the Hansen
cohesion parameters and how to determine them.
The Hansen cohesion parameters, .delta..sub.h and .delta..sub.p,
for selected polyhydric alcohols are displayed in Table I, below.
The Hansen and Beerbower data as reported in the CRC Handbook were
used when available. For diols that were not listed, the values
were calculated from group contributions using the Hansen and
Beerbower data as shown in the CRC Handbook, pp. 85-87 and
Kirk-Othmer, pp. 891-892. The values for .delta..sub.p were
calculated by the simple additive method as suggested in
Kirk-Othmer.
TABLE I ______________________________________ HANSEN PARAMETERS OF
DIHYDRIC ALCOHOLS ABBREVIA- DIOL TION .delta..sub.p .delta..sub.h
______________________________________ ETHYLENE GLYCOL EG 11.0 26.0
1,2-PROPANEDIOL 1,2-PD 9.4 23.3 1,3-PROPANEDIOL 1,3-PD 14.0 23.2
1,2-BUTANEDIOL 1,2-BD 7.7 20.8 1,3-BUTANEDIOL 1,3-BD 10.0 21.5
1,4-BUTANEDIOL 1,4-BD 10.0 21.5 2,3-BUTANEDIOL 2,3-BD 7.7 20.8
1,6-HEXANEDIOL 1,6-HD 8.4 17.8 2,5-HEXANEDIOL 2,5-HD 8.4 17.8
1,8-OCTANEDIOL 1,8-OD 6.3 15.5 1,10-DECANEDIOL 1,10-DD 5.0 13.8
DIETHYLENE GLYCOL DEG 14.7 20.5 POLYETHYLENE GLYCOL PEG 400 11.6
14.5 (400 mw) POLYETHYLENE GLYCOL PEG 1000 10.9 12.6 (1000 mw)
DIPROPYLENE GLYCOL DPG 20.3 18.4 TRIPROPYLENE GLYCOL TPG 9.8 16.1
POLYPROPYLENE GLYCOL PPG 400 8.3 12.9 (400 mw)
______________________________________
The data presented in Table I is displayed as a plot of
.delta..sub.h versus .delta..sub.p in FIG. 1.
The monomer mixture used in the process of the invention contains a
hydrophilic monomer such as HEMA as the major component, one or
more cross-linking monomers, and optionally small amounts of other
monomers such as methacrylic acid. HEMA is the preferred
hydrophilic monomer. Other hydrophilic monomers that can be
employed include 2-hydroxyethyl acrylate, 2-hydroxypropyl
methacrylate, 2-hydroxypropyl acrylate, 3-hydroxypropyl
methacrylate, N-vinyl pyrrolidone, glycerol mono-methacrylate,
glycerol mono-acrylate, and the like. The cross-linking monomers
that can be employed, either singly or in combination, include
ethylene glycol dimethacrylate, trimethylolpropane trimethacrylate,
glycerol trimethacrylate, polyethylene glycol dimethacrylate
(wherein the polyethylene glycol has a molecular weight up to,
e.g., about 400), and other polyacrylate and polymethacrylate
esters. The cross-linking monomer is used in the usual amounts,
e.g., from about 0.1 to about 3, and preferably in amounts of from
about 0.2 to about 2, parts by weight per 100 parts by weight of
HEMA or other hydrophilic monomer. Other monomers that can be used
include methacrylic acid, which is used to influence the amount of
water that the hydrogel will absorb at equilibrium. Methacrylic
acid is usually employed in amounts of from about 0.2 to about 8
parts, by weight, per 100 parts of HEMA. Other monomers that can be
present in the polymerization mixture include methoxyethyl
methacrylate, acrylic acid, and the like.
As was mentioned above, one of the features of the invention is
that hydrophobic monomers may be included in the monomer mixture
without encountering incompatibility problems to the degree that
such problems are encountered with prior art methods of
polymerizing HEMA-based copolymers. Illustrative of such
hydrophobic monomers are the UV-absorbing monomers such as
benzotriazole (meth)acrylate esters, for instance, the
2-[2'-hydroxy-5'-acryloyloxyalkylphenyl]-2H-benzotriazoles
disclosed by Beard et al. in U.S. Pat. No. 4,528,311, the
2-[2'-hydroxy-5'-acryloyloxy-alkoxyphenyl]-2H-benzotriazoles
disclosed by Dunks et al. in U.S. Pat. No. 4,716,234, and the
2-(2'-hydroxyphenyl)-5(6)-(acryloylalkoxy)benzotriazoles disclosed
by Dunks et al. in U.S. patent application Ser. No. 21,096, filed
on Mar. 3, 1987, and assigned to an affiliate of the assignee of
this application. Specific illustrative benzotriazole UV-absorbing
(meth)acrylate esters that can be used in the invention include the
following compounds:
2-(2'-hydroxy-5'-methacryloxyethylphenyl)-2H-benzotriazole;
2-(2'-hydroxy-5'-methacryloxyethylphenyl)-5-chloro-2H-benzotriazole;
2-(2'-hydroxy-5'-methacryloxypropylphenyl)-5-chloro-2H-benzotriazole;
2-(2'-hydroxy-5'-methacryloxypropyl-3'-tert-butylphenyl)-2H-benzotriazole;
2-(2'-hydroxy-5'-methacryloxypropyl-3'-tert-butylphenyl)-5-chloro-2H-benzot
riazole;
2-[2'-hydroxy-5'-(2-methacryloyloxyethoxy)-3'-tertbutylphenyl]-5-methoxy-2H
-benzotriazole;
2-[2'-hydroxy-5'-(gamma-methacryloyloxypropoxy)-3'-tert-butylphenyl]-5-meth
oxy-2H-benzotriazole; and
2-(3'-t-butyl-2'-hydroxy-5'-methoxyphenyl)-5-(3'-methacryloyloxypropoxy)ben
zotriazole.
Other hydrophobic monomers that can be included in the
polymerization reaction mixture for various purposes include
benzophenone derivatives, long chain alkyl (meth)acrylates, such as
n-dodecyl methacrylate, stearyl methacrylate, n-octyl methacrylate,
n-dodecyl acrylate, and the like.
The benzotriazole UV-absorbing (meth)acrylate esters are used in
the monomer mixture in an amount effective to absorb UV radiation
in the finished lens product. Usually, the proportion of the
UV-absorbing monomer will be within the range of from about 1 to
about 10 parts by weight per 100 parts by weight of the major
hydrophilic monomer(s) such as HEMA.
A polymerization catalyst is included in the monomer mixture. The
polymerization catalyst can be a free radical generating compound
such as lauroyl peroxide, benzoyl peroxide, isopropyl percarbonate,
azobisisobutyronitrile, or the like, that generate free radicals at
moderately elevated temperatures, or the polymerization catalyst
can be a photoinitiator system such as an aromatic alpha-hydroxy
ketone or a tertiary amine plus a diketone. Illustrative examples
of photoinitiator systems are 4-(2-hydroxyethoxy)phenyl
2-hydroxy-2-propyl ketone and a combination of camphorquinone and
ethyl 4-(N,N-dimethylamino)benzoate. The catalyst is used in the
polymerization reaction mixture in catalytically effective amounts,
e.g., from about 0.1 to about 2 parts by weight per 100 parts of
HEMA.
The examples set forth below illustrate the practice of the
invention.
EXAMPLE 1
Illustrative molding procedure
Contact lenses are molded from the following polymerization
reaction mixture:
______________________________________ Component Parts, by Weight
______________________________________ HEMA 100.0 Methacrylic acid
2.00 Ethylene glycol dimethacrylate 0.4 Darocure 1173.sup.(1) 0.35
1,4-butanediol Boric Acid Ester.sup.(2) 102.75
______________________________________ .sup.(1)
4-(2-hydroxyethoxy)phenyl 2hydroxy-2-propyl ketone .sup.(2)
Produced by reacting 797 parts, by weight, of 1,4butanediol with
203 parts, by weight, of boric acid at a temperature of 90.degree.
C. for 4 hours under 750 mm Hg vacuum.
The polymerization reaction mixture is placed in transparent
polystyrene molds of the type described in Larsen, U.S. Pat. No.
4,640,489 (see, especially, FIG. 2 of the Larsen patent), and is
exposed on one side of the Polystyrene mold to 1.7 Joules/cm.sup.2
of ultraviolet radiation for 6 to 12 minutes (the exact exposure
time is not narrowly critical).
EXAMPLE 2
Illustrative monomer/diluent recipe for UV-absorbing lens
Using conditions analogous to those described above in Example 1,
contact lenses are molded from the following polymerization
reaction mixture:
______________________________________ Component Parts, by Weight
______________________________________ HEMA 100.00 Methacrylic acid
2.04 Ethylene glycol dimethacrylate 0.4
2-(2'hydroxy-5'-methacryloxypropyl- 3.00 3'-
.sub.-t-butylphenyl)-5-chloro- 2H--benzotriazole Camphorquinone
0.40 Ethyl 4-(N,N--dimethylamino)benzoate 0.60 1,4-butanediol Boric
Acid Ester.sup.(1) 77.45 ______________________________________
.sup.(1) Produced by reacting 797 parts, by weight, of
1,4butanediol with 203 parts, by weight, of boric acid at a
temperature of 90.degree. C. for 4 hours under a vacuum of 750 mm
Hg.
EXAMPLE 3
A series of esters of boric acid and dihydric alcohols were made by
the following general procedure:
The boric acid and dihydric alcohol were charged to a 1-liter
rotating evaporator and gradually heated to 90.degree. C. (the time
to achieve 90.degree. C. was about 1 hour), while applying mild
vacuum (100 torr). When 90.degree. C. was reached, a full vacuum
(10 torr) was applied and the reaction was continued for 3 hours at
90.degree. C. After cooling, water content was determined by Karl
Fischer titration and the viscosity of the borate ester at
30.degree. C. was determined by a Brookfield LVF viscometer (6, 12,
and 30 rpm).
The borate esters that were prepared in accordance with the
foregoing general procedure are identified in Table II, below. The
table identifies the diols used, using the abbreviations mentioned
in Table I, and one triol, glycerol ("gly"), that was used as a
control, the mols of each component (alcohol and boric acid) and
the molar ratio of the alcohol to boric acid reactants used to
Prepare each ester, the viscosity at 30.degree. C. (in mPa Sec),
and the per cent of water in the ester. A column for comments is
also included in the table.
TABLE II ______________________________________ Mo- For 1000 lar
gms of ratio, Reactants alc Water Visc., Acid Alc to cont., mPa sec
Com- Run Alcohol Mols Mols acid % 30.degree. C. ments
______________________________________ 1 EG 3.75 12.38 3.30 0.5
Paste 2 EG 4.36 11.77 2.70 1.7 solid (1) 3 1,2-PD 3.91 9.97 2.55
0.3 85 4 1,2-PD 5.03 9.05 1.80 0.7 200 5 1,2-PD 5.68 8.52 1.50 1.4
632 (2) 6 1,3-PD 3.45 10.34 3.00 0.7 38 7 1,3-PD 5.68 8.52 1.50 1.4
40 8 1,2-BD 3.28 8.85 2.70 0.2 50 9 1,2-BD 5.08 7.61 1.5 1.1 100
(2) 10 1,3-BD 5.08 7.61 1.50 1.0 100 11 1,4-BD 3.01 9.03 3.00 1.8
1200 12 1,4-BD 3.28 8.85 2.70 1.4 14000 13 2,3-BD 3.28 8.85 2.70 0
48 14 2,3-BD 5.08 7.61 1.50 1.1 50 (2) 15 1,6-HD 2.63 7.09 2.70 0.3
27250 (3) 16 2,5-HD 2.40 7.21 3.00 0.4 15200 (3) 17 2,5-HD 2.63
7.09 2.70 0.4 100000+ (2),(3) 18 1,8-OD 2.09 5.96 2.85 0.3 solid
(1),(3) 19 1,10-DD 1.88 5.07 2.70 0.3 solid (4) 20 GLY 4.06 8.13
2.00 0.6-1 18-22000 21 DEG 2.87 7.75 2.7 1.3 870 22 PEG 400 0.88
2.36 2.70 0.7 590 23 PEG 1000 0.362 0.978 2.70 0.7 Solid (1) 24 DPG
2.36 6.37 2.70 1.3 2360 25 DPG 2.75 6.19 2.25 1.5 100000+ 26 TPG
1.72 4.65 2.70 0.9 1000 27 PPG 400 1.04 2.34 2.25 0.9 900 (4)
______________________________________ (1) Diluent solid, but
useable when mixed with monomers. (2) Boric acid crystals formed
when mixed with water. (3) Not completely compatible with water (in
a mixture of part ester to 1 parts water, by weight), but can be
used because it is displaceable after a wash with ethanol or a
mixture of ethanol and water. (4) Not compatible with either water
or monomer mixture (1:1 monomer:diluent, by weight); cannot be
used.
Many of the borate esters identified above in Table II were
evaluated as water-displaceable diluents with the following monomer
formulation:
______________________________________ Component Parts, by Weight
______________________________________ HEMA 100.0 Methacrylic acid
2.0 Ethylene glycol dimethacrylate 0.4 Darocure 1173 0.35 Diluent
102.75 ______________________________________
This monomer formulation, which contains 0.4 part of cross-linking
monomer, was selected for evaluation because the Young's modulus
values of the hydrogels prepared from this formulation can be
correlated well with expected performance in the contact lens
application. It has been found that if the Young's modulus of a
hydrogel prepared using this formulation (which includes 0.4 part
of a polyfunctional cross-linking monomer) is at least about
0.10-0.12 MPa, then a hydrogel prepared from a similar formulation,
which may contain a slightly higher proportion of cross-linking
monomer, can be expected to be strong enough for use as a soft
contact lens. In conventional commercial practice, the amount of
polyfunctional cross-linking monomer(s) such as ethylene glycol
dimethacrylate and trimethylolpropane trimethacrylate is normally
from about 0.2-1.0 part in a formulation similar to that used in
this Example.
Soft contact lenses were prepared from the monomer/diluent mixtures
set forth above in transparent polystyrene molds as described above
in Example 1. The monomer/diluent mixture in each mold was exposed
on one side to about 1.7 Joules/cm.sup.2 of ultraviolet radiation
for 10 minutes at 55.degree. C. (TL09 lamps, with peak radiation at
350 nm).
The lenses prepared from the diluent/monomer mixtures were
evaluated for:
(1) Appearance of lens, both in the mold and after demolding;
and
(2) Young's modulus of the hydrated lens; and
(3) Force required to demold the molded lenses.
The results of these evaluations are displayed in Tables III and
IV, below. Table III displays the Run No., the dihydric alcohol
used to make the borate ester diluent, lens appearance (C=clear,
W=white, OS=opaque surface, SO=slightly opaque), and the Young's
modulus "E", in MPa. Table IV displays the force required to demold
the molded lenses at three different temperatures.
TABLE III ______________________________________ EVALUATION OF
MOLDED LENSES Ester Appearance No Alcohol Mold Final E Comments
______________________________________ 1 EG C C .20 2 EG C C .23 3
1,2-PD C C .11 4 1,2-PD C C .18 5 1,2-PD C C/OS .17 (1) 7 1,3-PD --
C/OS -- (2) 8 1,2-BD C C .25 9 1,2-BD OS -- -- (2) 10 1,3-BD OS --
-- (2) 11 1,4-BD C C .24 13 2,3-BD C C .08 14 2,3-BD OS -- -- (2)
15 1,6-HD C C .19 16 2,5-HD C C .19 18 1,8-OD C SO .21 20 GLY C C
.25 (control) 21 DEG C C .29 22 PEG 400 C C .34 23 PEG 1000 C C .30
24 DPG C C .28 25 DPG C C .27 26 TPG C C .27 27 PPG 400 W W --
______________________________________ (1) Dissolved the
polystyrene mold slightly which caused a slightly opaqu surface.
(2) Dissolved the polystyrene mold; could not be demolded.
Modulus test
The Young's modulus values of the lenses displayed in Table III
were determined by the following procedure:
Scope
This test is useful for comparative non-destructive modulus testing
of lenses of almost identical physical dimensions. The test has
been calibrated against similar lenses tested in an accurate test
as described in Larsen et al., U.S. Pat. No. 4,680,336 (column
9-10).
Lenses
The lenses useful in this test are a -1.0 diopter, 8.9+/-0.3 mm BC
(base curve), 0.15+/-0.01 mm center thickness, 14.0+/-0.5 mm
diameter.
Test
The lens dimensions are measured and, if within the specification,
the lens is placed on top of a transparent acrylic cylinder (13 mm
outer diameter, 9.8 mm inner diameter, 7.2 mm height) so that the
lens front curve rests against the inner (9.8 mm diameter) top
surface of the acrylic cylinder. The set-up is immersed in 0.9%
saline in the center thickness-measuring chamber of an Optimec
JCF/R/SI Contact Lens Analyzer. The cylinder and lens are centered
so that the lens is in a horizontal position, and the center
thickness scale is adjusted so that it can measure deflection on
the center of the front curve surface.
A 3 mm stainless steel ball (weight 0.2584 gram) is carefully
placed on the concave side of the lens. The central part of the
lens will deflect depending on the modulus of the lens. The
deflection is read in mm on the center thickness scale, and the
modulus can be determined from the calibration graph, FIG. 2.
A minimum of 3 lenses from the same batch are being tested, and the
deflection of each lens is measured 3 times. The modulus is the
average of at least 9 measurements.
TABLE IV ______________________________________ Demold Force Ester
Demold Force (lbs) No. Diol 30.degree. C. 55.degree. C. 80.degree.
C. ______________________________________ 1 EG 6.49 (1.11) 5.15
4.76 (1.08) 2 EG (1) N/A (2) 6.15 (0.54) 3 1,2-PD 3.94 (0.43) 2.87
(0.52) 2.73 (0.52) 4 1,2-PD 4.53 (0.32) 3.20 (0.42) 3.26 (0.75) 5
1,2-PD 1.46 (0.77) 1.99 (0.87) 2.39 (1.03) 6 1,3-PD 3.95 (0.38)
3.11 (0.63) 2.68 (0.25) 7 1,3-PD (3) (3) (3) 10 1,3-BD (3) (3) (3)
11 1,4-BD 4.99 (0.63) 4.51 (0.47) 3.44 (0.53) 12 1,4-BD 5.70 (0.33)
3.91 (0.91) 3.50 (0.31) 20 GLY (1) (1) (1) 21 DEG 2.81 (0.66) 2.42
(0.71) 1.56 (0.64) 22 PEG 400 3.39 (0.36) 2.76 (0.51) 1.36 (0.43)
23 PEG 1000 3.47 (1.01) 3.53 (0.57) 3.03 (0.71) 24 DPG 0.86 (0.49)
1.08 (0.41) 1.18 (0.18) 25 DPG 0.92 (0.21) 0.76 (0.32) 1.11 (0.52)
26 TPG 1.75 (0.57) 1.76 (0.61) 2.18 (0.35) 27 TPG (4) (4) (4)
______________________________________ The numbers in parentheses
are standard deviations. (1) The flange on the top half of the mold
broke during force measurement (2) Data not available (3) Not
possible to demold. The polymer/diluent mixture dissolved the mol
and bonded the two halves of the mold together. (4) Demold force
too low to measure.
Demold test
The test employed to evaluate the force required to open the mold
in which the polymer/diluent mixtures were produced, the results of
which are displayed in Table IV, is as follows:
Scope
This test is useful for quantifying the minimum force required to
separate the front and back halves of the mold (as described in
Larsen, U.S. Pat. No. 4,640,489) which are bound together by a
polymer matrix containing some known level of diluent. The mold
dimensions should remain constant for all samples analyzed.
Instrumentation
The test fixture and assembly used to measure the forces to open
the molds is shown in FIG. 3. The instrument used for measuring the
force is a laboratory tensile testing apparatus 10, such as an
Instron model #1122. A 50 lb load cell (not shown) is used with the
chart recorder 12 being set at 20 lbs full scale.
The temperature is controlled by a heat gun (not shown), such as a
Varitemp heat gun (Model VT-750A) connected to a Staco type 3PN2210
rheostat. A T-type thermocouple (not shown) inserted in the
polymer/diluent mixture is used to measure the temperature of the
polymer/diluent mixture.
A fixture 14 holds the specimen 16 in place during the test and a
lever 18 is used to pull the top half 20 of the mold away from the
bottom half 22.
Test Procedure
The specimen is comprised of the top 20 and bottom 22 halves of the
mold 16, which are bound together by the polymer/diluent matrix 24.
The specimens for testing are freshly Produced filled molds of
constant dimensions. The molds are placed in a dessicator
immediately after polymerization so as to prevent moisture from
being absorbed by the polymer or the diluent.
The specimen to be tested is placed in the sample holder as shown
in FIG. 3. The sample fixture is held by the lower grip of the
Instron with a pressure of 36 PSI. The entire specimen is situated
at a 20.degree. angle to the horizontal plane when placed in the
fixture. The bottom half 22 of the mold is kept in place during the
test by inserting four pins (only two are shown, in cross-section)
26, 28 around the circumference of the bottom half 22 of the mold
at 90.degree. intervals.
The lever 18 used to pull the top half 20 away from the bottom half
22 is positioned between the two halves and is held in place by the
upper grip 30 of the Instron. The rate at which the lever pulls the
top half is controlled by the cross-head speed of the Instron.
The air flow of the heat gun is directed directly at the top half
of the mold to maintain consistent heating. The temperature of the
air flow can be controlled with the rheostat.
The sample temperature is monitored by inserting a thermocouple in
such a way as to measure the change in temperature of the
polymer/diluent matrix 24. When the thermocouple measures the
desired temperature, the cross-head of the Instron is raised at a
speed of 1 inch/min. The force to demold was measured at
30.degree., 55.degree., and 80.degree. C.
The force required to break the adhesion of the polymer/diluent to
the top half 20 as a function of time if recorded by the chart
recorder of the Instron. From this recording, the minimum demold
force is determined.
From the data presented above, it can be seen that only those
esters made from diols falling within the defined Hansen parameter
area give transparent lenses (which is essential for the contact
lens application), and only those having viscosities greater than
100 MPa sec have modulus values high enough to be strong enough to
be used in the contact lens application.
The demold data clearly demonstrate that the diol esters of this
invention give much easier demoldability (less force needed to
demold) than do the preferred esters of the Larsen patent, No.
4,495,313.
As an illustration of the yield improvement that can be obtained by
employing the diol-borate esters of this invention in place of a
glycerol-borate ester, the number of surface flaws was determined
on three batches of 80 lenses from each of monomer/ester mixtures,
using a formulation analogous to that set forth above in Example 1.
When the diluent used was a diethylene glycol/boric acid ester
(ester No. 21 in Table II), the percentage of surface defects was
found to be 10.4%, when the diluent was a 1,4-butanediol/boric acid
ester (ester No. 12 in Table II), the percentage of surface defects
was found to be 13.0%, and when the diluent was a glycerol/boric
acid ester (ester No. 20 in Table II), the percentage of surface
defects was found to be 30.4%. This is a valuable improvement over
the process taught in the Larsen patent, No. 4,495,313.
* * * * *